Process for the hydration of olefins

ABSTRACT

There is provided a process for converting light olefin to alcohol(s), ether(s) or mixtures of alcohol(s) and ether(s) which comprises contacting a feed containing at least one light olefin with water in the vapor and/or liquid phase under olefin hydration conditions in the presence of MCM-36 as olefin hydration catalyst to produce said alcohol(s) and/or ether(s).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related to copending U.S. application Ser. No. 07/811,360, filed Dec. 20, 1991, which is a continuation-in-art of copending U.S. application Ser. No. 07/776,718, filed Oct. 15, 1991, which is a continuation of U.S. application Ser. No. 07/640,330, filed Jan. 11, 1991, now abandoned.

BACKGROUND

The present invention relates to a process for the catalytic hydration of olefins to provide alcohols, ethers or their mixtures. More particularly, the invention relates to a process for the hydration of light olefins such as ethylene, propylene, butenes, pentenes, hexenes, heptenes, etc., and their mixtures to provide alcohols and/or ethers employing the acidic form of the synthetic porous MCM-36 material as catalyst. The alcohols and/or ethers are useful, inter alia, as high octane blending stocks for gasoline.

There is a need for an efficient catalytic process to manufacture alcohols and ethers from light olefins thereby augmenting the supply of high octane blending stocks for gasoline. Lower molecular weight alcohols and ethers such as isopropyl alcohol (IPA) and diisopropyl ether (DIPE) are in the gasoline boiling range and are known to have a high blending octane number. In addition, by-product propylene from which IPA and DIPE can be made is usually available in a fuels refinery. Light olefin streams containing mixtures of olefins in the C₂ to C₇ molecular weight range are also usually available, and the conversion of such streams or fractions thereof to alcohols and/or ethers can also provide products useful as solvents and as blending stocks for gasoline.

The catalytic hydration of olefins to provide alcohols and ethers is a well-established art and is of significant commerical importance. Representative olefin hydration processes are disclosed in U.S. Pat. Nos. 2,162,913; 2,477,380; 2,797,247; 3,798,097; 2,805,260; 2,830,090; 2,861,045; 2,891,999; 3,006,970; 3,198,752; 3,810,849; and 3,989,762, among others.

Olefin hydration employing zeolite catalysts is known. As disclosed in U.S. Pat. No. 4,214,107, lower olefins, in particular, propylene, are catalytically hydrated over a crystalline aluminosilicate zeolite catalyst having a silica to alumina ratio of at least 12 and a Constraint Index of from 1 to 12, e.g., HZSM-5 zeolite, to provide the corresponding alcohol, essentially free of ether and hydrocarbon by-product.

According to U.S. Pat. No. 4,499,313, an olefin is hydrated to the corresponding alcohol in the presence of hydrogen-type mordenite or hydrogen-type zeolite Y each having a silica-alumina molar ratio of 20 to 500. The use of such a catalyst is said to result in higher yields of alcohol than olefin hydration processes which employ conventional solid acid catalysts. Use of the catalyst is said to offer the advantage over ion-exchange type olefin hydration catalysts of not being restricted by the hydration temperature. Reaction conditions employed in the process include a temperature of from 50°-300° C., preferably 100°-250° C., a pressure of 5 to 200 kg/cm² to maintain liquid phase or gas-liquid multi-phase conditions and a mole ratio of water to olefin of from 1 to 20. The reaction time can be 20 minutes to 20 hours when operating batchwise and the liquid hourly space velocity (LHSV) is usually 0.1 to 10 in the case of continuous operation.

U.S. Pat. No. 4,611,086 describes the hydration of olefins to provide aliphatic alcohols employing natural or synthetic offretite as catalyst.

European Patent Application 210,793 describes an olefin hydration process employing a medium pore zeolite as hydration catalyst. Specific catalysts mentioned are Theta-1, said to be preferred, ferrierite, ZSM-22, ZSM-23 and NU-10.

Japanese laid-open application 60-246,335 describes the hydration of branched olefins in the presence of finely powdered zeolite catalyst.

SUMMARY

There is provided a process for converting light olefin to alcohol(s), ether(s) or mixtures thereof which comprises contacting a feed consisting essentially of at least one light olefin with water and an olefin hydration catalyst in the vapor and/or liquid phase under olefin hydration conditions to provide said alcohol(s) and/or ether(s), said olefin hydration catalyst comprising a synthetic porous MCM-36 material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction pattern of an as-synthesized form of a layered material which may be swollen and pillared,

FIG. 2 is an X-ray diffraction pattern of a swollen form of the material having the X-ray diffraction pattern shown in FIG. 1.

FIG. 3 is an X-ray diffraction pattern of the pillared form of the layered material having the X-ray diffraction pattern shown in FIG. 1.

FIG. 4 is an X-ray diffraction pattern of the calcined form of the swollen material having the X-ray diffraction pattern shown in FIG. 2.

EMBODIMENTS

The alcohol(s), ether(s) or mixtures thereof resulting from the foregoing olefin hydration process are advantageously employed as blending components for gasoline and as cosolvents for methanol to be incorporated into gasoline among other applications.

The present invention is applicable to the hydration of individual light olefins and mixtures of olefins of various structures, preferably within the C₂ -C₇ range. Accordingly, the invention is applicable to the hydration of mixtures of ethylene, propylene, butenes, pentenes, heptenes, heptenes, mixtures of these and other olefins such as gas plant off-gas containing light olefins, fluidized catalytic cracked (FCC) light gasoline containing pentenes, hexenes and heptenes, refinery FCC propane/propylene streams, etc. For example, a typical FCC light olefin stream possesses the following composition:

    ______________________________________                                         Typical Refinery FCC Light Olfein Composition                                                Wt. % Mole %                                                     ______________________________________                                         Ethane          3.3     5.1                                                    Ethylene        0.7     1.2                                                    Propane         14.5    15.3                                                   Propylene       42.5    46.8                                                   Isobutane       12.9    10.3                                                   n-Butane        3.3     2.6                                                    Butenes         22.1    18.32                                                  Pentanes        0.7     0.4                                                    ______________________________________                                    

The process of the invention is especially applicable to the conversion of propylene to mixtures of IPA and DIPE.

The operating conditions of the olefin hydration process herein are not especially critical and include a temperature of from about 50° to 300° C., preferably from about 90° to about 250° C. and most preferably from about 110° to about 220° C., a total system pressure of at least from about 5 atmospheres and preferably at least about 20 atmospheres and water to olefin mole ratio of from about 0.1 to about 30, preferably from about 0.2 to about 15 and most preferably from about 0.3 to about 5.

The olefin hydration process of this invention can be carried out under liquid phase, vapor phase or mixed vapor-liquid phase conditions in batch or continuous manner using a stirred tank reactor or fixed bed flow reactor, e.g., trickle-bed, liquid-up-flow, liquid-down-flow, counter-current, co-current, etc. Reaction times of from about 20 minutes to about 20 hours when operating in batch and an LHSV of from about 0.1 to about 10 volumes of liquid olefin per volume of catalyst per hour when operating continuously are suitable. When the olefin is introduced into the reactor as a gas, a gas hourly space velocity corresponding to an equivalent contact time, as obtained from the above-mentioned LHSV, may be employed. It is generally preferable to recover any unreacted olefin and recycle it to the reactor.

MCM-36 and methods for its preparation are described in the aforementioned U.S. application Ser. No. 07/811,360, filed Dec. 20, 1991, the entire disclosure of which is expressly incorporated herein by reference.

MCM-36 may be prepared from an intermediate material which is crystallized in the presence of a hexamethyleneimine directing agent and which, if calcined, without being swollen would be transformed into a material having an X-ray diffraction pattern as shown in Table 1.

                  TABLE 1                                                          ______________________________________                                         Interplanar   Relative Intensity,                                              d-Spacing (A) I/I.sub.o × 100                                            ______________________________________                                         30.0 ± 2.2 w-m                                                              22.1 ± 1.3 w                                                                12.36 ± 0.2                                                                               m-vs                                                             11.03 ± 0.2                                                                               m-s                                                              8.83 ± 0.14                                                                               m-vs                                                             6.86 ± 0.14                                                                               w-m                                                              6.18 ± 0.12                                                                               m-vs                                                             6.00 ± 0.10                                                                               w-m                                                              5.54 ± 0.10                                                                               w-m                                                              4.92 ± 0.09                                                                               w                                                                4.64 ± 0.08                                                                               w                                                                4.41 ± 0.08                                                                               w-m                                                              4.25 ± 0.08                                                                               w                                                                4.10 ± 0.07                                                                               w-s                                                              4.06 ± 0.07                                                                               w-s                                                              3.91 ± 0.07                                                                               m-vs                                                             3.75 ± 0.06                                                                               w-m                                                              3.56 ± 0.06                                                                               w-m                                                              3.42 ± 0.06                                                                               vs                                                               3.30 ± 0.05                                                                               w-m                                                              3.20 ± 0.05                                                                               w-m                                                              3.14 ± 0.05                                                                               w-m                                                              3.07 ± 0.05                                                                               w                                                                2.99 ± 0.05                                                                               w                                                                2.82 ± 0.05                                                                               w                                                                2.78 ± 0.05                                                                               w                                                                2.68 ± 0.05                                                                               w                                                                2.59 ± 0.05                                                                               w                                                                ______________________________________                                    

The values in this Table and like tables presented hereinafter were determined by standard techniques. The radiation was the K-alpha doublet of copper and a diffractometer equipped with a scintillation counter and an associated computer was used. The peak heights, I, and the positions as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on the computer associated with the diffractometer. From these, the relative intensities, 100 I/I_(o), where I_(o) is the intensity of the strongest line or peak, and d (obs.) the interplanar spacing in Angstrom Units (A), corresponding to the recorded lines, were determined. In Tables 1-8, the relative intensities are given in terms of the symbols w=weak, m=medium, s=strong and vs=very strong. In terms of intensities, these may be generally designated as follows:

    ______________________________________                                                 w =   0-20                                                                     m =  20-40                                                                     s =  40-60                                                                     vs =  60-100                                                           ______________________________________                                    

The material having the X-ray diffraction pattern of Table 1 is known as MCM-22 and is described in U.S. Pat. No. 4,954,325, the entire disclosure of which is incorporated herein by reference. This material can be prepared from a reaction mixture containing sources of alkali or alkaline earth metal (M), e.g., sodium or potassium, cation, an oxide of trivalent element X, e.g., aluminum, an oxide of tetravalent element Y, e.g., silicon, an organic (R) directing agent, hereinafter more particularly described, and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:

    ______________________________________                                         Reactants      Useful   Preferred                                              ______________________________________                                         YO.sub.2 /X.sub.2 O.sub.3                                                                      10-80   10-60                                                  H.sub.2 O/YO.sub.2                                                                              5-100  10-50                                                  OH.sup.-- /YO.sub.2                                                                           0.01-1.0 0.1-0.5                                                M/YO.sub.2     0.01-2.0 0.1-1.0                                                R/YO.sub.2     0.05-1.0 0.1-0.5                                                ______________________________________                                    

In the synthesis method for preparing the material having the X-ray diffraction pattern of Table 1, the source of YO₂ must be comprised predominately of solid YO₂, for example at least about 30 wt.% solid YO₂ in order to obtain the desired crystal product. Where YO₂ is silica, the use of a silica source containing at least about 30 wt.% solid silica, e.g., Ultrasil (a precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated SiO₂ containing about 87 wt.% silica, about 6 wt.% free H₂ O and about 4.5 wt.% bound H₂ O of hydration and having a particle size of about 0.02 micron) favors crystal formation from the above mixture and is a distinct improvement over the synthesis method taught in U.S. Pat. No. 4,439,409. If another source of oxide of silicon e.g., Q-Brand (a sodium silicate comprised of about 28.8 wt.% SiO₂, 8.9 wt.% Na₂ O and 62.3 wt.% H₂ O) is used, crystallization yields little or none of the crystalline material having the X-ray diffraction pattern of Table 1. Impurity phases of other crystal structures, e.g., ZSM-12, are prepared in the latter circumstance. Preferably, therefore, the YO₂, e.g., silica, source contains at least about 30 wt.% solid YO₂, e.g., silica, and more preferably at least about 40 wt.% solid YO₂, e.g., silica.

Crystallization of the crystalline material having the X-ray diffraction pattern of Table 1 can be carried out at either static or stirred conditions in a suitable reactor vessel, such as for example, polypropylene jars or teflon lined or stainless steel autoclaves. The total useful range of temperatures for crystallization is from about 80° C. to about 225° C. for a time sufficient for crystallization to occur at the temperature used, e.g., from about 24 hours to about 60 days. Thereafter, the crystals are separated from the liquid and recovered.

The organic directing agent for use in synthesizing the present crystalline material from the above reaction mixture may be hexamethyleneimine which has the following structural formula: ##STR1## Other organic directing agents which may be used include 1,4-diazacycloheptane, azacyclooctane, aminocyclohexane, aminocycloheptane, aminocyclopentane, N,N,N-trimethyl-1-adamantanammonium ions, and N,N,N-trimethyl-2-adamantanammonium ions. In general, the organic directing agent may be selected from the group consisting of heterocyclic imines, cycloalkyl amines and adamantane quaternary ammonium ions.

It should be realized that the reaction mixture components can be supplied by more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the crystalline material will vary with the nature of the reaction mixture employed and the crystallization conditions.

Synthesis of crystals may be facilitated by the presence of at least 0.01 percent, e.g., 0.10 percent or 1 percent, seed crystals (based on total weight) of crystalline product.

The crystalline material having the X-ray diffraction pattern of Table 1 passes through an intermediate stage. The material at this intermediate stage has a different X-ray diffraction pattern than that set forth in Table 1. It has further been discovered that this intermediate material is swellable with the use of suitable swelling agents such as cetyltrimethylammonium compounds, e.g., cetyltrimethylammonium hydroxide. However, when this swollen intermediate material is calcined, even under mild conditions, whereby the swelling agent is removed, the material can no longer be swollen with such swelling agent. By way of contrast it is noted that various layered silicates such as magadiite and kenyaite may be swellable with cetyltrimethylammonium compounds both prior to and after mild calcination.

The present swollen products may have relatively high interplanar distance (d-spacing), e.g., greater than about 6 Angstrom, e.g., greater than about 10 Angstrom and even exceeding 30 Angstrom. These swollen materials may be converted into pillared materials. These pillared materials, particularly silica pillared materials, may be capable of being exposed to severe conditions such as those encountered in calcining, e.g., at temperatures of about 450° C. for about two or more hours, e.g., four hours, in nitrogen or air, without significant decrease, e.g., less than about 10%, in interlayer distance.

The material having the X-ray diffraction pattern of Table 1, when intercepted in the swellable, intermediate state, prior to final calcination, may have the X-ray diffraction pattern shown in Table 2.

                  TABLE 2                                                          ______________________________________                                         d(A)                   I/I.sub.o                                               ______________________________________                                         13.53 ± 0.2         m-vs                                                    12.38 ± 0.2         m-vs                                                    11.13 ± 0.2         w-s                                                     9.15 ± 0.15         w-s                                                     6.89 ± 0.15         w-m                                                     4.47 ± 0.10         w-m                                                     3.95 ± 0.08         w-vs                                                    3.56 ± 0.06         w-m                                                     3.43 ± 0.06         m-vs                                                    3.36 ± 0.05         w-s                                                     ______________________________________                                    

An X-ray diffraction pattern trace for an example of such an as-synthesized, swellable material is shown in FIG. 1. A particular example of such an as-synthesized, swellable material is the material of Example 1 of the aforementioned U.S. Pat. No. 4,954,325. This material of Example 1 of U.S. Pat. No. 4,954,325 has the X-ray diffraction pattern given in the following Table 3.

                  TABLE 3                                                          ______________________________________                                         2 Theta        d(A)    I/I.sub.o × 100                                   ______________________________________                                         3.1            28.5    14                                                      3.9            22.7    <1                                                      6.53           13.53   36                                                      7.14           12.38   100                                                     7.94           11.13   34                                                      9.67           9.15    20                                                      12.85          6.89     6                                                      13.26          6.68     4                                                      14.36          6.17     2                                                      14.70          6.03     5                                                      15.85          5.59     4                                                      19.00          4.67     2                                                      19.85          4.47    22                                                      21.56          4.12    10                                                      21.94          4.05    19                                                      22.53          3.95    21                                                      23.59          3.77    13                                                      24.98          3.56    20                                                      25.98          3.43    55                                                      26.56          3.36    23                                                      29.15          3.06     4                                                      31.58          2.833    3                                                      32.34          2.768    2                                                      33.48          2.676    5                                                      34.87          2.573    1                                                      36.34          2.472    2                                                      37.18          2.418    1                                                      37.82          2.379    5                                                      ______________________________________                                    

Taking into account certain modifications, this swellable material may be swollen and pillared by methods generally discussed in the aforementioned U.S. Pat. No. 4,859,648, the entire disclosure of which is expressly incorporated herein be reference. The present modifications are discussed hereinafter and include the selection of proper swelling pH and swelling agent.

Upon being swollen with a suitable swelling agent, such as a cetyltrimethylammonium compound, the swollen material may have the X-ray diffraction pattern shown in Table 4.

                  TABLE 4                                                          ______________________________________                                         d(A)                   I/I.sub.o                                               ______________________________________                                         >32.2                  vs                                                      12.41 ± 0.25        w-s                                                      3.44 ± 0.07        w-s                                                     ______________________________________                                    

The X-ray diffraction pattern of this swollen material may have additional lines with a d(A) spacing less than the line at 12.41 ±0.25, but none of said additional lines have an intensity greater than the line at the d(A) spacing of 12.41±0.25 or at 3.44±0.07, whichever is more intense. More particularly, the X-ray diffraction pattern of this swollen material may have the lines shown in the following Table 5.

                  TABLE 5                                                          ______________________________________                                         d(A)                   I/I.sub.o                                               ______________________________________                                         >32.2                  vs                                                      12.41 ± 0.25        w-s                                                     11.04 ± 0.22        w                                                       9.28 ± 0.19         w                                                       6.92 ± 0.14         w                                                       4.48 ± 0.09         w-m                                                     3.96 ± 0.08         w-m                                                     3.57 ± 0.07         w-m                                                     3.44 ± 0.07         w-s                                                     3.35 ± 0.07         w                                                       ______________________________________                                    

Even further lines may be revealed upon better resolution of the X-ray diffraction pattern. For example, the X-ray diffraction pattern may have additional lines at the following d(A) spacings (intensities given in parentheses): 16.7±4.0 (w-m); 6.11±0.24 (w); 4.05±0.08 (w); and 3.80±0.08 (w).

In the region with d<9 A, the pattern for the swollen material is essentially like the one given in Table 2 for the unswollen material, but with the possibility of broadening of peaks.

An X-ray diffraction pattern trace for an example of such a swollen material is shown in FIG. 2. The upper profile is a 10-fold magnification of the lower profile in FIG. 2.

Upon being pillared with a suitable polymeric oxide, such as polymeric silica, the swollen material having the X-ray diffraction pattern shown in Table 4 may be converted into a material having the X-ray diffraction pattern shown in Table 6.

                  TABLE 6                                                          ______________________________________                                         d(A)                   I/I.sub.o                                               ______________________________________                                         >32.2                  vs                                                      12.38 ± 0.25        w-m                                                      3.42 ± 0.07        w-m                                                     ______________________________________                                    

The X-ray diffraction pattern of this pillared material may have additional lines with a d(A) spacing less than the line at 12.38±0.25, but none of said additional lines have an intensity greater than the line at the d(A) spacing of 12.38±0.25 or 3.42±0.07, whichever is more intense. More particularly, the X-ray diffraction pattern of this pillared material may have the lines shown in the following Table 7.

                  TABLE 7                                                          ______________________________________                                         d(A)                   I/I.sub.o                                               ______________________________________                                         >32.2                  vs                                                      12.38 ± 0.25        w-m                                                     10.94 ± 0.22        w-m                                                     9.01 ± 0.18         w                                                       6.88 ± 0.14         w                                                       6.16 ± 0.12         w-m                                                     3.93 ± 0.08         w-m                                                     3.55 ± 0.07         w                                                       3.42 ± 0.07         w-m                                                     3.33 ± 0.07         w-m                                                     ______________________________________                                    

Even further lines may be revealed upon better resolution of the X-ray diffraction pattern. For example, the X-ray diffraction pattern may have additional lines at the following d(A) spacings (intensities given in parentheses): 5.59±0.11 (w); 4.42±0.09 (w); 4.11±0.08 (w); 4.04±0.08 (w); and 3.76±0.08 (w).

An X-ray diffraction pattern trace for an example of such a pillared material is given in FIG. 3. The upper profile is a 10-fold magnification of the lower profile in FIG. 3.

If the material swollen with a suitable swelling agent is calcined without prior pillaring another material is produced. For example, if the material which is swollen but not pillared is calcined in air for 6 hours at 540° C., a very strong line at a d(A) spacing of greater than 32.2 will no longer be observed. By way of contrast, when the swollen, pillared material is calcined in air for 6 hours at 540° C., a very strong line at a d(A) spacing of greater than 32.2 will still be observed, although the precise position of the line may shift.

An example of a swollen, non-pillared material, which has been calcined, has the pattern as shown in Table 8.

                  TABLE 8                                                          ______________________________________                                         2 Theta       d(A)    I/I.sub.o × 100                                    ______________________________________                                         3.8           23.3    12                                                       7.02          12.59   100                                                      8.02          11.02   20                                                       9.66          9.16    14                                                       12.77         6.93    7                                                        14.34         6.18    45                                                       15.75         5.63    8                                                        18.19         4.88    3                                                        18.94         4.69    3                                                        19.92         4.46    13         broad                                         21.52         4.13    13         shoulder                                      21.94         4.05    18                                                       22.55         3.94    32                                                       23.58         3.77    16                                                       24.99         3.56    20                                                       25.94         3.43    61                                                       26.73         3.33    19                                                       31.60         2.831   3                                                        33.41         2.682   4                                                        34.62         2.591   3          broad                                         36.36         2.471   1                                                        37.81         2.379   4                                                        ______________________________________                                    

The X-ray powder pattern shown in Table 8 is similar to that shown in Table 1 except that most of the peaks in Table 8 are much broader than those in Table 1.

An X-ray diffraction pattern trace for an example of the calcined material corresponding to Table 8 is given in FIG. 4.

As mentioned previously, the calcined material corresponding to the X-ray diffraction pattern of Table 1 is designated MCM-22. For the purposes of the present disclosure, the pillared material corresponding to the X-ray diffraction pattern of Table 6 is designated herein as MCM-36. The swollen material corresponding to the X-ray diffraction pattern of Table 4 is designated herein as the swollen MCM-22 precursor. The as-synthesized material corresponding to the X-ray diffraction pattern of Table 2 is referred to herein, simply, as the MCM-22 precursor.

The layers of the swollen material of this disclosure may have a composition involving the molar relationship:

    X.sub.2 O.sub.3 :(n)YO.sub.2'

wherein X is a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum, Y is a tetravalent element such as silicon and/or germanium, preferably silicon, and n is at least about 5, usually from about 10 to about 150, more usually from about 10 to about 60, and even more usually from about 10 to about 40.

To the extent that the layers of the swollen MCM-22 precursor and MCM-36 have negative charges, these negative charges are balanced with cations. For example, expressed in terms of moles of oxides, the layers of the swollen MCM-22 precursor and MCM-36 may have a ratio of 0.5 to 1.5 R₂ O:X₂ O_(3') where R is a monovalent cation or 1/m of a cation of valency m.

MCM-36 adsorbs significant amounts of commonly used test adsorbate materials, i.e., cyclohexane, n-hexane and water. Adsorption capacities for this pillared material, especially the silica pillared material, may range at room temperature as follows:

    ______________________________________                                         Adsorbate    Capacity, Wt. Percent                                             ______________________________________                                         n-hexane     17-40                                                             cyclohexane  17-40                                                             water        10-40                                                             ______________________________________                                    

wherein cyclohexane and n-hexane sorption are measured at 20 Torr and water sorption is measured at 12 Torr.

The swellable material, used to form the swollen material of the present disclosure, may be initially treated with a swelling agent. Such swelling agents are materials which cause the swellable layers to separate by becoming incorporated into the interspathic region of these layers. The swelling agents are removable by calcination, preferably in an oxidizing atmosphere, whereby the swelling agent becomes decomposed and/or oxidized.

Suitable swelling agents may comprise a source of organic cation, such as quaternary organoammonium or organophosphonium cations, in order to effect an exchange of interspathic cations. Organoammonium cations, such as n-octylammonium, showed smaller swelling efficiency than, for example, cetyltrimethylammonium. A pH range of 11 to 14, preferably 12.5 to 13.5 is generally employed during treatment with the swelling agent.

The as-synthesized material is preferably not dried prior to being swollen. This as-synthesized material may be in the form of a wet cake having a solids content of less than 30% by weight, e.g., 25 wt% or less.

The foregoing swelling treatment results in the formation of a layered oxide of enhanced interlayer separation depending upon the size of the organic cation introduced. In one embodiment, a series of organic cation exchanges can be carried out. For example, an organic cation may be exchanged with an organic cation of greater size, thus increasing the interlayer separation in a step-wise fashion. When contact of the layered oxide with the swelling agent is conducted in aqueous medium, water is trapped between the layers of the swollen species.

The organic-swollen species may be treated with a compound capable of conversion, e.g., by hydrolysis and/or calcination, to pillars of an oxide, preferably to a polymeric oxide. Where the treatment involves hydrolysis, this treatment may be carried out using the water already present in organic-swollen material. In this case, the extent of hydrolysis may be modified by varying the extent to which the organic-swollen species is dried prior to addition of the polymeric oxide precursor.

It is preferred that the organic cation deposited between the layers be capable of being removed from the pillared material without substantial disturbance or removal of the interspathic polymeric oxide. For example, organic cations such as cetyltrimethylammonium may be removed by exposure to elevated temperatures, e.g., calcination, in nitrogen or air, or by chemical oxidation preferably after the interspathic polymeric oxide precursor has been converted to the polymeric oxide pillars in order to form the pillared layered product.

These pillared layered products, especially when calcined, exhibit high surface area, e.g., greater than 500 m² /g, and thermal and hydrothermal stability making them highly useful as catalysts or catalytic supports, for hydrocarbon conversion processes, for example, alkylation.

Insertion of the organic cation between the adjoining layers serves to physically separate the layers in such a way as to make the layered material receptive to the interlayer addition of a polymeric oxide precursor. In particular, cetyltrimethylammonium cations have been found useful. These cations are readily incorporated within the interlayer spaces of the layered oxide serving to prop open the layers in such a way as to allow incorporation of the polymeric oxide precursor. The extent of the interlayer spacing can be controlled by the size of the organoammonium ion employed.

Interspathic oxide pillars, which may be formed between the layers of the propped or swollen oxide material, may include an oxide, preferably a polymeric oxide, of zirconium or titanium or more preferably of an element selected from Group IVB of the Periodic Table (Fischer Scientific Company Cat. No. 5-702-10, 1978), other than carbon, i.e., silicon, germanium, tin and lead. Other suitable oxides include those of Group VA, e.g., V, Nb, and Ta, those of Group IIA, e.g., Mg or those of Group IIIB, e.g., B. Most preferably, the pillars include polymeric silica. In addition, the oxide pillars may include an element which provides catalytically active acid sites in the pillars, preferably aluminum.

The oxide pillars are formed from a precursor material which may be introduced between the layers of the organic "propped" species as an ionic or electrically neutral compound of the desired elements, e.g., those of Group IVB. The precursor material may be an organometallic compound which is a liquid under ambient conditions. In particular, hydrolyzable compounds, e.g., alkoxides, of the desired elements of the pillars may be utilized as the precursors. Suitable polymeric silica precursor materials include tetraalkylsilicates, e.g., tetrapropylorthosilicate, tetramethylorthosilicate and, most preferably, tetraethylorthosilicate. Suitable polymeric silica precursor materials also include quaternary ammonium silicates, e.g., tetramethylammonium silicate (i.e. TMA silicate). Where the pillars also include polymeric alumina, a hydrolyzable aluminum compound can be contacted with the organic "propped" species before, after or simultaneously with the contacting of the propped layered oxide with the silicon compound. Preferably, the hydrolyzable aluminum compound employed is an aluminum alkoxide, e.g., aluminum isopropoxide. If the pillars are to include titania, a hydrolyzable titanium compound such as titanium alkoxide, e.g., titanium isopropoxide, may be used.

After calcination to remove the organic propping agent, the final pillared product may contain residual exchangeable cations. Such residual cations in the layered material can be ion exchanged by known methods with other cationic species to provide or alter the catalytic activity of the pillared product. Suitable replacement cations include cesium, cerium, cobalt, nickel, copper, zinc, manganese, platinum, lanthanum, aluminum, ammonium, hydronium and mixtures thereof.

Particular procedures for intercalating layered materials with metal oxide pillars are described in U.S. Pat. Nos. 4,831,005; 4,831,006; and 4,929,587. The entire disclosures of these patents are expressly incorporated herein by reference. U.S. Pat. No. 4,831,005 describes plural treatments with the pillar precursor. U.S. Pat. No. 4,929,587 describes the use of an inert atmosphere, such as nitrogen, to minimize the formation of extralaminar polymeric oxide during the contact with the pillar precursor. U.S. Pat. No. 4,831,006 describes the use of elevated temperatures during the formation of the pillar precursor.

The resulting pillared products exhibit thermal stability at temperatures of 450° C. or even higher as well as substantial sorption capacities (as much as 17 to 40 wt% for C₆ hydrocarbon). The pillared products may possess a basal spacing of at least about 32.2A and surface areas greater than 500 m² /g.

The layered material may be subjected to thermal treatment, e.g., to decompose organoammonium ions. This thermal treatment is generally performed by heating one of these forms at a temperature of at least about 370° C. for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is preferred simply for reasons of convenience.

Prior to its use as a catalyst, the MCM-36 should be subjected to thermal treatment to remove part or all of any organic constituent present therein.

MCM-36 can optionally be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such component can be associated chemically and/or physically with the MCM-36 and/or matrix with which the MCM-36 may be optionally composited. Thus, e.g., the hydrogenating component can be introduced into the catalyst composition by way of co-crystallization, exchanged into the composition to the extent a Group IIIA element, e.g., aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can be impregnated in, or on, the MCM-36 such as, for example, by, in the case of platinum, treating the MCM-36 with a solution containing the platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.

The MCM-36, especially in its metal, hydrogen and ammonium forms, can be beneficially converted to another form by thermal treatment. This thermal treatment is generally performed by heating one of these forms at a temperature of at least about 370° C. for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is preferred simply for reasons of convenience. The thermal treatment can be performed at a temperature of up to about 925° C.

Prior to its use as a catalyst, the MCM-36 crystals may be at least partially dehydrated. This can be accomplished by heating the MCM-36 to a temperature in the range of from about 200° C. to about 595° C. in an atmosphere such as air, nitrogen, etc., and at atmospheric, subatmospheric or superatmospheric pressures for a period of from between about 30 minutes to about 48 hours. Dehydration can also be performed at room temperature merely by placing the MCM-36 in a vacuum but a longer time will be required to achieve a suitable degree of dehydration.

The MCM-36 can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be provided in the form of a powder, a granule or a molded product such as an extrudate having a particle size sufficient to pass through a 2 mesh (Tyler) screen and be substantially retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded.

It may be desired to incorporate the MCM-36 with another material, i.e., a binder, which is resistant to the temperatures and other conditions employed in the isoparaffin alkylation process of this invention. Suitable binder materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter can be either naturally occurring or provided in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a binder material in conjunction with MCM-36, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst. Inactive materials suitably serve as diluents to control the amount of conversion so that reaction products can be obtained economically and in a controlled fashion without having to employ other means for controlling the rate of reaction. These materials can be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the MCM-36 under commercial operating conditions. Good crush strength is an advantageous attribute for commercial use since it prevents or delays breaking down of the catalyst into powder-like materials.

Naturally occurring clays which can be composited with MCM-36 crystals include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with MCM-36 also include inorganic oxides, notably alumina.

Apart from or in addition to the foregoing binder materials, the MCM-36 crystals can be composited with an inorganic oxide matrix such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, etc. It may be advantageous to provide at least a part of the foregoing matrix materials in colloidal form so as to facilitate extrusion of the bound catalyst component(s).

The relative proportions of finely divided MCM-36 and inorganic oxide matrix can vary widely with the MCM-36 content ranging from about 1 to about 95 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite.

In order to more fully illustrate the process of this invention and the manner of practicing same, the following examples are presented. In examples illustrative of the synthesis of MCM-36, whenever sorption data are set forth for comparison of sorptive capacities for water, cyclohexane and/or n-hexane, they were Equilibrium Adsorption values determined as follows:

A weighed sample of the calcined adsorbent was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to less than 1 mm Hg and contacted with 12 Torr of water vapor or 40 Torr of n-hexane or 40 Torr of cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at 90° C. The pressure was kept constant (within about ±0.5 mm Hg) by addition of adsorbate vapor controlled by a manostat during the adsorption period, which did not exceed about 8 hours. As adsorbate was adsorbed by the absorbent, the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapor to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was calculated as the adsorption capacity of the sample in g/100 g of calcined adsorbant.

EXAMPLE 1

A material which may be swollen and pillared was prepared as follows. Water, sodium hydroxide, sodium aluminate, silica (Ultrasil), and hexamethyleneimine (HMI) were combined in the following mole ratios:

    2.5 Na.sub.2 O:Al.sub.2 O.sub.3 :30 SiO.sub.2 :10 HMI:580 H.sub.2 O.

The reaction mixture was heated in an autoclave to 143° C. for 96 hours. The X-ray diffraction pattern for this material is shown pictorially in FIG. 1.

A mixture of 150 g of the wet cake (42% solids) and 1100 ml of 29% CTMA-OH (a 29% solution of cetyltrimethylammonium chloride that was contacted with hydroxide-for-halide exchange resin-one liter of the resin with 1.4 miliequivalent/ml exchange capacity per 3 liters of the solution) was reacted for 96 hours in a steambox. The product was filtered, washed twice with 400 ml of water and air dried overnight, yielding approximately 101 g of swollen product. Fifty grams of the swollen material was slurried with 300 g of TEOS and heated at 80° C. for 24 hours under a stream of nitrogen. After filtration and overnight drying, the product (56.60 g) was hydrolyzed in water for 4 hours, giving the pillared material (approximately 50 grams) containing 70% solids (based upon calcination at 540° C.). A portion (44.3 grams) of the pillared material was mixed with 23.3 g of Kaiser alumina (72.5% solids) and pelletized. The pellets were exchanged four times with 1 M ammonium nitrate (one hour contact followed by washing with 300 ml of water). The product was reformulated into pellets, dried at 110° C. for two hours and calcined in nitrogen for 3 hours and in air for 6 hours. Total product yield was approximately 41 grams of 65% MCM-36/35% Al₂ O₃.

EXAMPLE 2

This Example demonstrates the catalytic activity of the pelletized 65% MCM-36/35% Al₂ O₃ catalyst of Example 1 for a propylene hydration/etherification reaction. The evaluation was carried out in a fixed-bed unit using a feedstock consisting of H₂ O/C₃ =/IPA (14/66/20 wt%) at 1000 psig, 327° F. and 1.14 WHSV. IPA is co-fed with water and propylene to increase DIPE yield and improve catalyst stability. The catalyst performance is shown in Table 9. The results indicate that MCM-36 is active for propylene etherification, achieving about 8 wt% propylene conversion with 87% DIPE selectivity after 1 DOS.

EXAMPLE 3

In this Example, the propylene hydration evaluation was subsequently carried out after the propylene etherification experiment (Example 2). The feedstock consisted of only propylene and water (52:48 wt%) and the reactor temperature was varied from 330° to 380° F. The catalyst performance is shown in Table 10. MCM-36 achieved about 17 wt% propylene conversion with very high selectivity for IPA production (89%).

In Tables 9 and 10, the following abbreviations are used: C₃ = stands for propylene; IPA stands for isopropylalcohol; R×R stands for reactor; LHSV stands for liquid hourly space velocity; DIPE stands for diisopropylether; and C₆ = stands for hexene.

                  TABLE 9                                                          ______________________________________                                         Performance of MCM-36 for Propylene Hydration/Etherification                   Feedstock: C.sub.3 ═:H.sub.2 O: IPA (66:14:20 wt %)                                         Run No                                                                         1      2                                                      ______________________________________                                         Processing Conditions:                                                         Pressure, psig     1000     1000                                               Avg R × R Temp, °F.                                                                  327      327                                                LHSV               0.79     0.80                                               Time on Stream, Hr 24       47                                                 Conversion, wt %                                                               C.sub.3 ═      8.0      7.2                                                H.sub.2 O          13.1     11.8                                               Product Selectivity, wt %                                                      DIPE               87.4     81.9                                               IPA                10.9     17.0                                               C.sub.6 ═ (Dimer)                                                                             1.7      1.1                                                ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                         Performance of MCM-36 for Propylene Hydration                                  Feedstock: C.sub.3 ═:H.sub.2 O (52.48 wt %)                                             Run No                                                                         3       4         5                                               ______________________________________                                         Processing Conditions:                                                         Pressure, psig 1000      1000      1000                                        Avg R × R Temp, °F.                                                              329       329       380                                         LHSV           0.69      0.69      0.69                                        Time on Stream, Hrs                                                                           141       189       213                                         Mass Balance, wt %                                                                            95        99        98                                          Conversion, wt %                                                               C.sub.3 ═  17.6      16.8      27.8                                        H.sub.2 O      13.7      7.2       13.3                                        Product Selectivity, wt %                                                      DIPE           10.9      8.6       28.1                                        IPA            88.4      90.5      66.7                                        C.sub.6 ═ (Dimer)                                                                         0.7       0.9       5.2                                         ______________________________________                                     

What is claimed is:
 1. A process for converting light olefin to alcohol(s), ether(s) or mixtures thereof which comprises contacting a feed consisting essentially of at least one light olefin with water and an olefin hydration catalyst in the vapor and/or liquid phase under olefin hydration conditions to provide said alcohol(s) and/or ether(s), said olefin hydration catalyst comprising a synthetic porous crystalline MCM-36 material, said MCM-36 material being a pillared layered material having the following X-ray diffraction pattern

    ______________________________________                                                d(A)     I/I.sub.o                                                      ______________________________________                                                >32.2    vs                                                                    12.38 ± 0.25                                                                         w-m                                                                    3.42 ± 0.07                                                                         w-m                                                            ______________________________________                                    


2. A process according to claim 1, wherein the layers of the MCM- 36 have a composition comprising the molar relationship

    X.sub.2 O.sub.3 :(n)YO.sub.2'

wherein n is at least about 5, X is a trivalent element selected from the group consisting of aluminum, boron, gallium and combinations thereof, and Y is a tetravalent element selected from the group consisting of silicon, germanium and combinations thereof.
 3. A process according to claim 2, wherein X comprises aluminum and Y comprises silicon.
 4. A process according to claim 1, wherein said olefin hydration catalyst comprises said synthetic porous crystalline material and a matrix.
 5. A process according to claim 4, wherein said matrix is silica or alumina-containing material.
 6. A process according to claim 4, wherein said catalyst composition is in the form of extrudate, beads or fluidizable microspheres.
 7. A process according to claim 1, wherein the olefin feed contains a mixture of light olefins.
 8. A process according to claim 1, wherein the olefin component of the feed contains from two to seven carbon atoms.
 9. A process according to claim 1, wherein the olefin feed contains at least one olefin selected from the group consisting of ethylene, propylene, butenes, pentenes, hexenes and heptenes.
 10. A process according to claim 1, wherein the olefin feed contains propylene.
 11. A process according to claim 1, wherein the olefin feed contains butene.
 12. A process according to claim 1, wherein the olefin feed is naphtha cracker off-gas containing light olefins.
 13. A process according to claim 1, wherein the olefin feed is light catalytic cracked gasoline containing pentenes, hexenes and heptenes.
 14. A process according to claim 1, wherein said olefin hydration conditions comprise a temperature of from about 50° to about 300° C.
 15. A process according to claim 1, wherein said olefin hydration conditions comprise a total pressure of at least about 5 atmospheres.
 16. A process according to claim 1, wherein the mole ratio of water to total olefin is from about 0.1 to about
 30. 